Lithium metal is an ideal electrode material for future rechargeable lithium metal batteries. However, the widespread deployment of metallic lithium anode is significantly hindered by its dendritic growth and low Coulombic efficiency, especially in ester solvents. Herein, by rationally manipulating the electrolyte solvation structure with a high donor number solvent, enhancement of the solubility of lithium nitrate in an ester‐based electrolyte is successfully demonstrated, which enables high‐voltage lithium metal batteries. Remarkably, the electrolyte with a high concentration of LiNO3 additive presents an excellent Coulombic efficiency up to 98.8 % during stable galvanostatic lithium plating/stripping cycles. A full‐cell lithium metal battery with a lithium nickel manganese cobalt oxide cathode exhibits a stable cycling performance showing limited capacity decay. This approach provides an effective electrolyte manipulation strategy to develop high‐voltage lithium metal batteries.

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Calcium‐metal batteries (CMBs) provide a promising option for high‐energy and cost‐effective energy‐storage technology beyond the current state‐of‐the‐art lithium‐ion batteries. Nevertheless, the development of room‐temperature CMBs is significantly impeded by the poor reversibility and short lifespan of the calcium‐metal anode. A solvation manipulation strategy is reported to improve the plating/stripping reversibility of calcium‐metal anodes by enhancing the desolvation kinetics of calcium ions in the electrolyte. The introduction of lithium salt changes the electrolyte structure considerably by reducing coordination number of calcium ions in the first solvation shell. As a result, an unprecedented Coulombic efficiency of up to 99.1 % is achieved for galvanostatic plating/stripping of the calcium‐metal anode, accompanied by a very stable long‐term cycling performance over 200 cycles at room temperature. This work may open up new opportunities for development of practical CMBs.

The surface morphology of Li metal anode significantly dictates the stability and safety of Li metal batteries. The key parameters for morphological control and causes for dendritic growth of Li anode are still not clear. Although the plating kinetics is generally believed to be associated with Li growth habits, the detailed models are still not well defined. In this work, the temperature effect on the stability and efficiency of Li anode is systematically investigated in a variety of electrolyte composition for Li metal batteries. A dendrite‐free growth mechanism is observed, and a high Coulombic efficiency up to ≈99.4% in Li||Cu cells is achieved by tuning the deposition behaviors at elevated temperatures. The results provide insights into the Li dendrite growth mechanism and general principle for developing stable Li anode.